CN107473456A - A kind of integrated conduct method of acrylate industrial wastewater - Google Patents
A kind of integrated conduct method of acrylate industrial wastewater Download PDFInfo
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- CN107473456A CN107473456A CN201710930729.2A CN201710930729A CN107473456A CN 107473456 A CN107473456 A CN 107473456A CN 201710930729 A CN201710930729 A CN 201710930729A CN 107473456 A CN107473456 A CN 107473456A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/04—Acids; Metal salts or ammonium salts thereof
- C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/04—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste liquors, e.g. sulfite liquors
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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Abstract
The invention discloses a kind of integrated conduct method of acrylate industrial wastewater, comprise the following steps：A, other waste water in mixing acrylate production process in addition to catalyst water-washing waste water, obtain composite waste；B, the pH of composite waste obtained by step A is adjusted to after 68, adds chain-transferring agent, at 20 40 DEG C after stirring and dissolving, add initiator, be warming up to 45 85 DEG C, be incubated 4 10 hours and carry out polymerisation；Chain-transferring agent is at least one of aliphatic mercaptan, carbon tetrachloride, sodium formate, inorganic phosphate, octanol, isopropanol, propyl alcohol or butanol；C, step B resulting materials are cooled to room temperature, separating-purifying, obtain Sodium Polyacrylate.The present invention reduces the discharge capacity of acrylate industrial wastewater；Poly- (methyl) the PAA water resistance dirt significant effect lifting of gained；Cost is low；Pass through the selection of chain-transferring agent and separation method so that the Sodium Polyacrylate quality purity isolated is more than 90%, and molecular weight dispersity is compared with I below 1.2.
Description
Technical field
The present invention relates to a kind of integrated conduct method of acrylate industrial wastewater, belong to field of waste water treatment.
Background technology
(methyl) esters of acrylic acid waste water belongs to the industrial wastewater of difficult for biological degradation.From domestic and international research, for propylene
The processing method of acid and its esters waste water can be divided mainly into：Three kinds of Physical, chemical method and bioanalysis.From the point of view for the treatment of effect,
The physicochemical method Biochemical method effect that compares is much better.Processing for acrylicacidandesters class waste water, at present
More conventional method is burning method or discharged after diluting, but processing cost is too high, and causes considerable damage to local water environment,
Influence local resident's health of human body.With the further investigation of high-level oxidation technology in recent years, wet oxidation process has also been adopted
(WAO), at the processing method such as supercritical oxidation process (SCWO) and Fenton oxidation method, biological treatment, electrolytic-biological combined method
Acrylic compounds waste water is managed, but is all only limitted to the laboratory research stage, and the problem of more also be present.
Direct burning method is the main method of current domestic processing (methyl) acrylate industrial wastewater.Its technical process is
Waste water is passed through into pre- thermo-neutrality, the waste water after neutralization, which is heated, enters destilling tower steam heating concentrate, and recovery section technique is used
Water, heavy constituent (Liquid Residue) are sent into incinerator and burned.Water outlet pH value 10~11, COD after burning<100mg/L.Although burn
Method high treating effect, but its shortcoming is that processing cost is high, it is necessary to expend substantial amounts of fuel, the organic matter in waste water can not be sharp
With, and contain substantial amounts of inorganic salts in the waste water discharged, certain pollution can be caused to environment.Supercritical oxidation process (SCWO) and
Fenton oxidation method complex process, treatment effect fail to reach industrial technology requirement.
Catalytic wet air oxidation is that the U.S. is invented in the fifties.Acrylic compounds and esters waste water and compressed air pass through useless
Delivered to after water elevator pump and air compressor mixing and enter reactor after heat exchanger is heated to 200~250 DEG C, in HTHP
Organic matter in lower beds waste water is oxidized to carbon dioxide and water, and reaction product is discharged after water separates.This method
Although without consumption auxiliary fuel, the technological requirement carries out under higher temperature and pressure, and to water quality requirement compared with
Height, the different kinds of ions in waste water impurity can cause the permanent poisoning of catalyst, so being very restricted its application.
Biological treatment is mainly that waste water enters into acidification hydrolization after reconciling acidity into acidizing hydrolyzation tank, will be divided greatly
The organic matter of son changes into small organic molecule, and gets rid of a part of organic matter；The water outlet of hydrolytic tank enters two-stage and detested
Oxygen processing system carries out Anaerobic Treatment, removes most organic matter, and anaerobic effluent is further located by aerobic system
Reason, waste water can qualified discharge.Biological treatment is generally carried out at normal temperatures and pressures, and energy consumption is low, is greatly reduced (methyl)
The processing cost of acrylic compounds and its esters production waste water, and can also produce the gases such as methane that can be as the energy.But
Due to (methyl) acrylic compounds and its complicated component of esters production waste water, and the materials such as substantial amounts of S elements are usually contained to micro-
Biological growth has strong suppression and toxic action, therefore there is the shortcomings that fluctuation of service for biological treatment system.
CN1948189A discloses a kind of electrolytic-biological combined method processing acrylic acid production waste water.Acrylic acid is given birth to first
Production waste water is electrolysed, and adjusts pH5~7,8~9V of control voltage, 20~40A of electric current, 10~30min of electrolysis time.Will electrolysis
Waste water afterwards is diluted, and adjusts pH6.5~8, addition phosphate is handled subsequently into anaerobic reactor, by anaerobic reaction
Device effluent COD concentration control enters aerobic reactor after 200~1000mg/L, after processing water outlet can directly discharge.It is raw
Thing handling process can be carried out at normal temperatures and pressures, and energy consumption is relatively low, and can also produce can be as the methane gas of the energy.But
The composition of acrylic compounds and its esters waste water is more, wherein many materials contained have strong suppression and poison to microorganism growth
Evil effect, therefore biological treatment system there is fluctuation of service, time-consuming the shortcomings of.
CN101786742A discloses a kind of processing method of (methyl) acrylate industrial wastewater, and this method first uses carbonic acid
The pH value of sodium/sodium hydroxide regulation (methyl) acrylate industrial wastewater makes it pass through activated carbon layer to after 6~8
Filtering is pre-processed；Again chain-transferring agent is added into the waste water by pretreatment, stirring make solid dissolving and is warming up to 40~
90℃；Then the aqueous solution dissolved with initiator is added dropwise, is incubated 1~10 hour and carries out polymerisation；Reacted waste water cooling
By nanofiltration and/or Ultra filtration membrane component after to room temperature, part water is sloughed in separation and small molecule salt obtains poly- (methyl) third
Olefin(e) acid sodium water solution；This method can reduce the discharge capacity of waste water in (methyl) acrylate production process；It can also recycle
Poly- (methyl) aqueous sodium acrylate solution of (methyl) PAA production low molecule amount in waste water, is mainly used in dispersant, resistance
Dirty agent, cement water reducing agent.But preceding method exist gained poly- (methyl) PAA molecular weight distribution it is wider, decentralization compared with
Greatly, heterogeneity, for antisludging agent when effect difference the defects of.
The content of the invention
In order to solve the defects of acrylate industrial wastewater processing is present in the prior art, further solve
It is wider that molecular weight distribution existing for Sodium Polyacrylate obtained by low molecular weight sodium polyacrylate is produced in CN101786742A, decentralization
Larger, heterogeneity, purity are relatively low, and during for antisludging agent the defects of effect difference, the present invention provides a kind of acrylate industrial wastewater
Integrated conduct method.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows：
A kind of integrated conduct method of acrylate industrial wastewater, comprises the following steps：
A, other waste water in mixing acrylate production process in addition to catalyst water-washing waste water, obtain composite waste；
B, the pH of composite waste obtained by step A is adjusted to 6-8, adds chain-transferring agent, the stirring and dissolving at 20-40 DEG C
Afterwards, initiator is added, is warming up to 45-85 DEG C, insulation 4-9 hours carry out polymerisation；Chain-transferring agent is aliphatic mercaptan, four
At least one of chlorination carbon, sodium formate, inorganic phosphate, octanol, isopropanol, propyl alcohol or butanol；
C, step B resulting materials are cooled to room temperature, separating-purifying, obtain Sodium Polyacrylate.
The application acrylate includes methacrylate and acrylate.Sodium Polyacrylate includes sodium polymethacrylate
And Sodium Polyacrylate.It is the meaning not to be covered to be removed in step A.
The processing method of one kind (methyl) esters of acrylic acid production waste water of the invention, can not only reduce (methyl) acrylic acid
The discharge capacity of waste water in ester production process；Also recycle the poly- (first of (methyl) PAA production low molecule amount in waste water
Base) aqueous sodium acrylate solution, it is mainly used in antisludging agent.Part, which does not separate clean small molecule salt, does not influence the use of antisludging agent
Efficiency.
In step B pH is adjusted with sodium carbonate or sodium hydroxide etc..
The application is obviously improved the homogeneity of Sodium Polyacrylate molecular weight by the special selection to chain-transferring agent, from
And significantly improve the scale inhibition effect of product.
The integrated conduct method cost of the application acrylate industrial wastewater is low, pollution-free, and material is recycled, letter
Single easy to operate, reaction condition is gentle, stability is good.
Composite waste in step A is：Using methacrylic acid or acrylic acid with corresponding alcohol as raw material, metering system is produced
During acid esters or acrylate, solvent is taken out of in waste water and purification process in esterification process washing and/or alkaline cleaning procedure production
The mixed liquor of raw waste water.
In order to further improve the homogeneity and scale inhibition effect of gained Sodium Polyacrylate, the initiator in step B is over cure
It is sour ammonium, sodium peroxydisulfate, potassium peroxydisulfate, sodium hydrogensulfite, ammonium bisulfite, potassium bisulfite, hydrogen peroxide, frerrous chloride, different
At least two mixed initiator in cumene hydroperoxide or benzoyl peroxide, the quality dosage of initiator is in step A
The 2%-6% of gained composite waste quality.
It is preferred that if initiator includes two kinds of components, the mass ratio between two kinds of components is (1-2)：(1-2).
The quality dosage of chain-transferring agent in step B is the 1%-20% of gained composite waste quality in step A.Such energy
Further improve the homogeneity and scale inhibition effect of gained Sodium Polyacrylate.
As a kind of separation means of the application, in step C, separating-purifying uses nanofiltration and/or Ultra filtration membrane component
Separated, obtain Sodium Polyacrylate.
As another separation means of the application, in step C, separating-purifying uses solvent deposition method isolated poly- third
Olefin(e) acid sodium.
In order to improve separating effect, step C is, after step B resulting materials are cooled into room temperature, is concentrated into solid content as 30
± 10wt%, C1-C6 organic solvent is added, separate out Sodium Polyacrylate, be separated by filtration, filtering gained solid is polyacrylic acid
Sodium, for antisludging agent, filtering gained liquid is fractionated to obtain organic solvent and waste water, will be fractionated the organic solvent reuse of gained, will point
Evaporate the Waste water concentrating of gained, burn.
In order to further improve product yield, C1-C6 organic solvent is methanol, ethanol or acetone.
The NM technology of the present invention is with reference to prior art.
The beneficial effects of the invention are as follows：
1. the application reduces the discharge capacity of waste water in (methyl) acrylate production process；
2. poly- (methyl) aqueous sodium acrylate solution of (methyl) PAA production low molecule amount in waste water is recycled,
It is mainly used in antisludging agent；
3. compared to patent CN101786742A, the application need not carry out active carbon adsorption filtering and impurity removing to waste water, no
Waste residue activated carbon can be produced, not only reduces handling process, also saves the production cost of production Sodium Polyacrylate, it is not necessary to be useless
Slag activated carbon treatment cost；
4. compared to patent CN101786742A, the application is using chain tra nsfers such as aliphatic mercaptan, inorganic phosphate, octanols
Agent, it is smaller to produce the molecular weight dispersity of Sodium Polyacrylate, below 1.3, than more uniform；
5. compared to patent CN101786742A, the application uses solvent deposition method, and Sodium Polyacrylate is separated out and separated, is adopted
With being separated by filtration, solution fractionation reuse, the Sodium Polyacrylate quality purity isolated is more than 90%, and molecular weight dispersity is compared with I
Below 1.2, than more uniform；It can be used for antisludging agent, scale inhibition effect is obviously improved.
Brief description of the drawings
Fig. 1 is the process chart of the integrated conduct method of acrylate industrial wastewater of the present invention；
In figure, 1 alcohol solution, 2 bases solution, 3 acrylic acid wastewaters, 4 steam, 5 cooling water inlets, 6 dog-houses, 7 cool back
Water, 8 steam condensate (SC)s, 9 reaction vavuum pumps, 10 UF membrane feed pumps, 11 water or small molecule salt, 12 brine waste grooves, 13 films
Separator, 14 evaporation feed pumps, 15 2nd effect evaporators, 16 evaporative condensers, 17 evaporation in vacuo pumps, 18 alcohol solution reuses, 19
Two effect evaporation reboilers, 20 1 effect evaporation feed pumps, 21 1st effective evaporators, 22 1 effect evaporation reboilers, 23 1 effect evaporation dischargings
Pump, 24 burning disposals, 25 poly- (methyl) PAAs, 26 biochemical treatments.
Embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
Normal temperature refers to 25 ± 5 DEG C in embodiment.Sodium polyacrylate solution obtained by embodiment separating-purifying uses GBT 16632-
The measure of 2008 water treatment agent scale-inhibiting properties：Tosca method determines its scale-inhibiting properties.Using gel permeation chromatography JPC to it
Molecular weight and molecular weight distribution are detected.Mixing acrylate production waste water is to be removed in acrylate production process in each example
Other waste water beyond catalyst water-washing waste water, it is with corresponding alcohol as raw material using methacrylic acid or acrylic acid, produces methyl
During acrylate or acrylate, solvent is taken out of in waste water and purification process in esterification process washing and/or alkali cleaning
The mixed liquor of waste water caused by journey.
Embodiment 1
Take acrylate industrial wastewater (wherein PAA accounting is about 12~13%) 600g of solid content 15.5%, hydrogen
Sodium oxide molybdena adjusts pH to 6, the addition chain-transferring agent isopropanol 60g into composite waste, under normal temperature after stirring and dissolving, adds initiator
Benzoyl peroxide 6g, sodium hydrogensulfite 12g, it is warming up to 80 DEG C；Insulation carries out polymerisation in 4 hours, and reacted waste water is cold
But to after room temperature, passing sequentially through nanofiltration and Ultra filtration membrane component carries out separation water and small molecule salt obtains poly- (methyl) propylene
Acid sodium aqueous solution, Gu midnight from；Production goes out the molecular weight of Sodium Polyacrylate 4600, decentralization Mw/Mn=1.25, and purity is big
In 90%；Other waste water containing a small amount of PAA carry out heating concentration after separation, and fractionation isopropanol cools back uses during concentration, surplus
Remaining waste water heavy constituent is burned, and light component carries out biochemical treatment.Refer to technological process Fig. 1.Gained Sodium Polyacrylate it is relative
Scale inhibition efficiency 92.32%.
Embodiment 2
Take acrylate industrial wastewater (wherein PAA accounting is about 12~13%) 600g of solid content 15.5%, hydrogen
Sodium oxide molybdena adjusts pH to 8, the addition chain-transferring agent lauryl mercaptan 10g into composite waste, under normal temperature after stirring and dissolving, adds and triggers
Agent isopropyl benzene hydroperoxide 6g, potassium bisulfite 12g, is warming up to 50 DEG C；Insulation carries out polymerisation for 9 hours, reacted useless
After being water-cooled to room temperature, pass sequentially through nanofiltration and Ultra filtration membrane component carries out separation water and small molecule salt obtains poly- (methyl)
Aqueous sodium acrylate solution, Gu midnight from；Production goes out the molecular weight of Sodium Polyacrylate 5510, decentralization Mw/Mn=1.30, pure
Degree is more than 90%.Other waste water containing a small amount of PAA carry out heating concentration after separation, and heavy constituent is burned, and light component is entered
Row biochemical treatment.Refer to technological process Fig. 1.The relative scale inhibition efficiency 91.02% of gained Sodium Polyacrylate.
Embodiment 3
Acrylate industrial wastewater (wherein PAA accounting is about 12~13%) 600g of solid content 15.5% is taken, is used
Sodium carbonate adjusts pH to 6, the addition chain-transferring agent sodium phosphate 20g into composite waste, under normal temperature after stirring and dissolving, adds initiator
Sodium peroxydisulfate 6g, sodium hydrogensulfite 6g, hydrogen peroxide 12g, it is warming up to 80 DEG C；Insulation carries out polymerisation for 8 hours, reacted
After waste water is cooled to room temperature, the volume of decompression concentrated solution to 210ml about 1/3, fractionation butanol cools back uses during concentration, addition
100g ethanol, 0.5h is stirred, after standing 15min, poly- (methyl) PAA filter cake, Sodium Polyacrylate obtained by filter cake are obtained after press filtration
Molecular weight 3860, decentralization Mw/Mn=1.17, purity is more than 90%；By filtrate fractionation obtained by press filtration, the cooling of gained ethanol
Posterior circle uses (concentration fractionation then add solvent), and other waste water containing a small amount of PAA heat dense after fractionation recovery
Contracting, heavy constituent are burned, and light component carries out biochemical treatment.The relative scale inhibition efficiency 98.59% of gained Sodium Polyacrylate.
Embodiment 4
Acrylate industrial wastewater (wherein PAA accounting is about 12~13%) 600g of solid content 15.5% is taken, is used
Sodium carbonate adjusts pH to 8, the addition chain-transferring agent sodium formate 20g into composite waste, under normal temperature after stirring and dissolving, adds initiator
Ammonium persulfate 6g, ammonium bisulfite 6g, hydrogen peroxide 12g, it is warming up to 60 DEG C；Insulation carries out polymerisation for 8 hours, reacted
After waste water is cooled to room temperature, the volume of decompression concentrated solution to 210ml about 1/3, fractionation butanol cools back uses during concentration, addition
100g acetone, 0.5h is stirred, after standing 15min, poly- (methyl) PAA filter cake, Sodium Polyacrylate obtained by filter cake are obtained after press filtration
Molecular weight 3928, decentralization Mw/Mn=1.16, purity is more than 90%.By filtrate fractionation obtained by press filtration, the cooling of gained acetone
Posterior circle uses (concentration fractionation then add solvent), and other waste water containing a small amount of PAA heat dense after fractionation recovery
Contracting, heavy constituent are burned, and light component carries out biochemical treatment.The relative scale inhibition efficiency 98.93% of gained Sodium Polyacrylate.
Embodiment 5
Take acrylate industrial wastewater (wherein PAA accounting is about 12~13%) 600g of solid content 15.5%, hydrogen
Sodium oxide molybdena adjusts pH to 7, the addition chain-transferring agent butanol 60g into composite waste, under normal temperature after stirring and dissolving, adds initiator mistake
Sodium sulphate 6g, ammonium bisulfite 6g, isopropyl benzene hydroperoxide 6g, it is warming up to 60 DEG C；Insulation carries out polymerisation, reaction for 8 hours
After waste water afterwards is cooled to room temperature, the volume of decompression concentrated solution to 210ml about 1/3, fractionation butanol cools back use during concentration, adds
Enter 100g ethanol, stir 0.5h, after standing 15min, poly- (methyl) PAA filter cake, polyacrylic acid obtained by filter cake are obtained after press filtration
The molecular weight of sodium is 3860, decentralization Mw/Mn=1.17, and purity is more than 90%；Filtrate fractionation, gained ethanol obtained by press filtration is cold
But Posterior circle uses (concentration fractionation then add solvent), and other waste water containing a small amount of PAA heat dense after fractionation recovery
Contracting, heavy constituent are burned, and light component carries out biochemical treatment.The relative scale inhibition efficiency 98.85% of gained Sodium Polyacrylate.
Embodiment 6
Acrylate industrial wastewater (wherein PAA accounting is about 12~13%) 600g of solid content 15.5% is taken, is used
Sodium carbonate adjusts pH to 7, the addition chain-transferring agent octanol 60g into composite waste, under normal temperature after stirring and dissolving, adds initiator mistake
Ammonium sulfate 6g, ammonium bisulfite 6g, benzoyl peroxide 6g, it is warming up to 60 DEG C；Insulation carries out polymerisation in 8 hours, after reaction
Waste water be cooled to room temperature after, the volume of decompression concentrated solution to 210ml about 1/3, fractionation octanol cools back uses during concentration, addition
100g methanol, 0.5h is stirred, after standing 15min, poly- (methyl) PAA filter cake, Sodium Polyacrylate obtained by filter cake are obtained after press filtration
Molecular weight 3880, decentralization Mw/Mn=1.15, purity is more than 90%；By filtrate fractionation obtained by press filtration, the cooling of gained methanol
Posterior circle uses and (adds solvent after concentration fractionation).Other waste water containing a small amount of PAA heat dense after fractionation recovery
Contracting, heavy constituent are burned, and light component carries out biochemical treatment.The relative scale inhibition efficiency 99.04% of gained Sodium Polyacrylate.
Claims (8)
- A kind of 1. integrated conduct method of acrylate industrial wastewater, it is characterised in that：Comprise the following steps：A, the waste water in mixing acrylate production process in addition to catalyst water-washing waste water, obtains composite waste；B, the pH of composite waste obtained by step A is adjusted to 6-8, adds chain-transferring agent, at 20-40 DEG C after stirring and dissolving, Initiator is added, is warming up to 45-85 DEG C, insulation 4-9 hours carry out polymerisation；Chain-transferring agent is aliphatic mercaptan, tetrachloro Change at least one of carbon, sodium formate, inorganic phosphate, octanol, isopropanol, propyl alcohol or butanol；C, step B resulting materials are cooled to room temperature, separating-purifying, obtain Sodium Polyacrylate.
- 2. the method as described in claim 1：It is characterized in that：Composite waste in step A is：With methacrylic acid or propylene Sour with corresponding alcohol is raw material, during producing methacrylate or acrylate, in esterification process solvent take out of waste water and The mixed liquor of waste water caused by washing and/or alkaline cleaning procedure in purification process.
- 3. method as claimed in claim 1 or 2：It is characterized in that：Initiator in step B is ammonium persulfate, sodium peroxydisulfate, Potassium peroxydisulfate, sodium hydrogensulfite, ammonium bisulfite, potassium bisulfite, hydrogen peroxide, frerrous chloride, isopropyl benzene hydroperoxide or At least two in benzoyl peroxide, the quality dosage of initiator is the 2%-6% of gained composite waste quality in step A.
- 4. method as claimed in claim 1 or 2：It is characterized in that：The quality dosage of chain-transferring agent in step B is step A The 1%-20% of middle gained composite waste quality.
- 5. method as claimed in claim 1 or 2：It is characterized in that：In step C, separating-purifying uses nanofiltration and/or milipore filter Separation assembly is separated, and obtains Sodium Polyacrylate.
- 6. method as claimed in claim 1 or 2：It is characterized in that：In step C, separating-purifying is separated using solvent deposition method Obtain Sodium Polyacrylate.
- 7. method as claimed in claim 6：It is characterized in that：Step C is, dense after step B resulting materials are cooled into room temperature It is 30 ± 10wt% to be reduced to solid content, adds C1-C6 organic solvent, separates out Sodium Polyacrylate, is separated by filtration, and filtering gained is solid Body is Sodium Polyacrylate, is fractionated to obtain organic solvent and waste water for antisludging agent, filtering gained liquid, will be fractionated the organic molten of gained Agent reuse, by the Waste water concentrating for being fractionated gained, burn.
- 8. method as claimed in claim 7：It is characterized in that：C1-C6 organic solvent is methanol, ethanol or acetone.
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| CN110963647A (en) * | 2019-12-19 | 2020-04-07 | 安徽工程大学 | Treatment method of acrylic acid and lipid wastewater |
| CN111574648A (en) * | 2020-06-20 | 2020-08-25 | 南通百川新材料有限公司 | Synthetic method of sodium polyacrylate |
| CN112745418A (en) * | 2020-12-28 | 2021-05-04 | 江苏利田科技股份有限公司 | Method for preparing low-molecular-weight sodium polyacrylate by using wastewater generated in production of acrylic resin |
| CN113501611A (en) * | 2021-07-21 | 2021-10-15 | 上海泓济环保科技股份有限公司 | Recycling treatment method for tail water in butyl acrylate production |
| CN114394707A (en) * | 2021-12-20 | 2022-04-26 | 中海油天津化工研究设计院有限公司 | Process method for treating wastewater from acrylate production |
| CN114425319A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Wet oxidation catalyst and preparation method thereof |
| CN114716087A (en) * | 2022-04-11 | 2022-07-08 | 杭州胜澜科技有限公司 | Acrylic acid wastewater treatment method |
| CN114907031A (en) * | 2022-05-26 | 2022-08-16 | 昌德新材科技股份有限公司 | Cement raw material additive, application thereof and cement production process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786742A (en) * | 2010-02-09 | 2010-07-28 | 广东工业大学 | Treatment method of methacrylate or acrylate industrial wastewater |
| CN103408175A (en) * | 2013-07-22 | 2013-11-27 | 沈阳理工大学 | Treatment and reclamation method of (methyl) acrylic acid production wastewater |
| CN104277142A (en) * | 2014-08-22 | 2015-01-14 | 常州大学 | Production method of narrow-distribution low-molecular-weight polymers |
-
2017
- 2017-10-09 CN CN201710930729.2A patent/CN107473456B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101786742A (en) * | 2010-02-09 | 2010-07-28 | 广东工业大学 | Treatment method of methacrylate or acrylate industrial wastewater |
| CN103408175A (en) * | 2013-07-22 | 2013-11-27 | 沈阳理工大学 | Treatment and reclamation method of (methyl) acrylic acid production wastewater |
| CN104277142A (en) * | 2014-08-22 | 2015-01-14 | 常州大学 | Production method of narrow-distribution low-molecular-weight polymers |
Non-Patent Citations (6)
| Title |
|---|
| 中国环境保护产业协会: "《国家重点环境保护实用技术及示范工程汇编 2009》", 31 December 2009, 中国环境科学出版社 * |
| 吉鹤立: "《中国食品添加剂及配料使用手册》", 30 June 2016, 中国质检出版社 * |
| 郑晓宇等: "《油田化学品》", 31 January 2001, 化学工业出版社 * |
| 陆柱等: "《水处理技术》", 31 December 2000, 华东理工大学出版社 * |
| 陈甘棠: "《聚合反应工程基础》", 30 June 1991, 中国石化出版社 * |
| 韩哲文: "《高分子科学教程》", 31 December 2001, 华东理工大学出版社 * |
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|---|---|---|---|---|
| CN110963647A (en) * | 2019-12-19 | 2020-04-07 | 安徽工程大学 | Treatment method of acrylic acid and lipid wastewater |
| CN111574648A (en) * | 2020-06-20 | 2020-08-25 | 南通百川新材料有限公司 | Synthetic method of sodium polyacrylate |
| CN114425319A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Wet oxidation catalyst and preparation method thereof |
| CN114425319B (en) * | 2020-10-15 | 2023-08-04 | 中国石油化工股份有限公司 | Wet oxidation catalyst and preparation method thereof |
| CN112745418A (en) * | 2020-12-28 | 2021-05-04 | 江苏利田科技股份有限公司 | Method for preparing low-molecular-weight sodium polyacrylate by using wastewater generated in production of acrylic resin |
| CN113501611A (en) * | 2021-07-21 | 2021-10-15 | 上海泓济环保科技股份有限公司 | Recycling treatment method for tail water in butyl acrylate production |
| CN114394707A (en) * | 2021-12-20 | 2022-04-26 | 中海油天津化工研究设计院有限公司 | Process method for treating wastewater from acrylate production |
| CN114716087A (en) * | 2022-04-11 | 2022-07-08 | 杭州胜澜科技有限公司 | Acrylic acid wastewater treatment method |
| CN114907031A (en) * | 2022-05-26 | 2022-08-16 | 昌德新材科技股份有限公司 | Cement raw material additive, application thereof and cement production process |
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